Waxlike substances and method of preparing the same



Patented Jan. 2, 1934 WAXLIKE SUBSTANCES AND METHOD-OF PREPARING THE SAME Donald K. Tressler and Carlisle Schade, Pittsburgh, Pa., assignors to The Mathieson Alkali Works, Inc., New York, N. Y., a corporation of Virginia No Drawimns Application August 14; 1929 erial No. 385,979

18 Claims. (01. 260-134) This invention relates to improvements in the production of higher hydroxy ketones, and includes new hydroxy ketones as new products, and a process of producing the same.

The ketones produced from the higher unsaturated fatty acids, and from mixtures of unsaturated and saturated fatty acids, are, for the most part, relatively soft, low melting products of limited usefulness.

According to the present invention, such unsaturated ketones, produced from unsaturated fatty acids, or mixtures of ketones produced from mixtures of' saturated and unsaturated fatty acids, are converted into hard wax-like 1| products, 1. e., hydroxy ketones, or mixtures of hydroxy ketones and saturated ketones. The conversion of the unsaturated, ketones into hydroxy ketones is effected by treatment with sulfuric acid to convert the unsaturated ketones into ethereal sulfates, and then hydrolvzing these ethereal sulfates to produce the hydroxy ketones.

We have found that when unsaturated ketones, such as oleone, dissolved in acid washed naphtha, or other suitable solvent, is treated with concentrated sulfuric acid, the ketone is converted into the ethereal sulfate, and that the ethereal sulfate so produced can be hydrolyzed with boiling water or steam to form the hydroxy ketone, which, in the case of the treatment of oleone is di-hydroxy stearone.

The ketones which are employed in the present process for producingthe new hydroxy ketones are those derived from unsaturated higher fatty acids, such as oleic acid, linolic acid. Instead of using the individual unsaturated fatty acids, mixtures may be employed, or mixtures of saturated and unsaturated fatty acids, such as are obtained by the saponiflcation of animal or vegetable oils or fats. The unsaturated fatty acids, or mixtures of unsaturated and saturated fatty acids, can readily be converted into ketones of high purity and with high yields by heating to a high temperature, around 300 C. or higher, in the presence of a small amount of a suitable catalyst such as finely divided iron or iron oxide,

and under non-oxidizing conditions, i. e., with avoidance of the presence of air during the process.

The reaction can readily be carried out with exclusion of air by passing a current of inert gas through the reaction vessel to sweep out the air before the reaction mixture is heated to a high temperature, and by continuing the passage of inert gas through the apparatus during the g process to insure that air will be excluded.

By carrying out the process under non-oxidizing conditions, the absorption of oxygen by the hot unsaturated fatty acids is substantially prevented, the formation of objectionable tarry byproducts is minimized, and a high yield of the ketones is produced. Oleic acid, for example, can be heated at 310 C. for about two and onehalf hours with 5 to 10% of finely divided oxide of iron and an inert gas bubbled through the apparatus and the reaction mixture to sweep out 5 the air. From oleic acid, a high yield of oleone can be thus produced. Mixed ketones can be prepared by heating two or more unsaturated fatty acids with iron or iron oxide in absence of air,

or by heating a mixture of saturated and unsaturated fatty acids in a similar manner. This improved method of producing ketones from unsaturated fatty acids, or from mixtures of unsaturated and saturated-fatty acids, forms the subject matter of a separate application of D. K. 76 Tressler, Serial No. 556,322, filed August 10, 1931.

In carrying out the present process, we find it of advantage to employ a solvent for the ketones such as acid washed naphtha, i. e. naphtha freed from olefins, or ethyl ether, or other solvent which does not react with sulfuric acid, but which will serve as a solvent for the ketones. Crude or recrystallized oleone, for example, when dissolved in twice its volume or more of acid washed naphtha, will. react nearly quantitatively with sulfuric acid of -or higher concentration. Crude oleone may also be melted and stirred directly into concentrated sulfuric acid and oleone sulfuric acid obtained, but the yield is somewhat lower. If acid washed naphtha is used as a solvent for the oleone, the oleone sulfuric acid separates from the naphtha, which may then be removed by decantation.

The ethereal sulfate produced by the treatment of the ketone with sulfuric acid may be hydrolyzed, for example, by slowly pouring the ethereal sulfate into boiling water or by introducing hot water or steam into the ketone ethereal sulfate or into the solution. For example, the hydrolysis of the oleone sulfuric acid may be eflected by pouring the oleone sulfuric acid into boiling water, or by introducing hot water or steam into the oleone sulfuric acid or its solution. In either to which a material such as'magnesite may be added to neutralize the acid, or repeated boiling or washing with water may be employed to ,effect the removal of the acid.

The crude di-hydroxy stearone, after freeing from acid, solidifies on cooling as a firm wax, melting, for example, around 60 C. Although this crude product is fairly hard, it is somewhat greasy to the feel and may be kneaded withthe fingers. Upon crystallization from naphtha, ethyl acetate or some other suitable organic solvent, a hard, brittle, non-tacky mass is obtained melting at about 74 C.

The ketones derived from erucic, linolic, and other unsaturated fatty acids may be converted into hydroxy ketones by the same general procedure above indicated. Mixed ketones, produced from mixtures of saturated and unsaturated fatty acids, when treated according to the present process, yield hydroxy ketones admixed with saturated ketones possessing especially desirablev properties as substitutes for hard waxes or softer waxes, or waxes of intermediate properties, for example, as substitutes for Chinese insect wax in making polishes, etc.

The invention will be further illustrated by the following more detailed description and specific examples, but it will be understood that the invention is not limited thereto.' The parts are by weight.

100 parts of ketone, mainly oleone and other unsaturated ketones, prepared from 125 parts of double distilled red oil in the manner above referred to, was dissolved in 500 parts of naphtha which had previously been freed from olefins by careful washing with sulfuric acid. This solution was placed in a water jacketed vessel and rapidly agitated with-a mechanical stirrer. parts of sulfuric acid was added slowly, with continued rapid agitation and cooling, so that the reaction mixture did not become hot. After thorough agitation the solution was allowed to stand until the ethereal sulfate and admixed sulfuric acid had settled to the bottom of the reaction vessel. The supernatant naphtha was decanted and purified by redistillation and made available for reuse. The mixture of ethereal sulfate and sulfuric acid was immediately poured into 1000 parts of boiling water. After boiling about one hour, the solution was allowed to cool and the aqueous layer poured off and discarded. 1000 parts of boiling water was then added, together with magnesite to neutralize the sulfuric acid and the solution was boiled until all of the free acid had been washed out of the crude dihydroxy stearone. If a neutralizing agent such as magnesite is not employed, repeated washings may be necessary to effect complete removal of the excess acid.

By proceeding according to the above example, we have produced about parts of crude dihydroxy stearone from 100 parts of unsaturated ketones. The crude di-hydroxy stearone is somewhat greasy in character and may be too greasy for many purposes where a harder wax-like product is required. It can be purified by fractional crystallization and converted into a hard, brittle, wax-like product. This can be accomplished,

for example, by dissolving 100 parts of the crude di-hydroxy stearone in about 140 parts of hot ethyl acetate and crystallizing it therefrom.

The following example will further illustrate the invention as applied to a mixture of ketones prepared from unsaturated and saturated fatty acids, and to produce therefrom a mixture of furic acid was slowly added. The solution was then run slowly into 1500 parts of boiling water.- A viscous emulsion formed which was slow in breaking. After boiling about two hours, the solution was allowed to cool and the aqueous layer discarded. 1000 parts of boiling water together with magnesite were added and the water boiled until all the free acid had been washed out of the product.

The product produced according to this example is a mixture of ketones containing di-hydroxy stearone, mono-hydroxy .stearone, etc. The stearone present in the mixture of ketones prepared from stearic and commercial oleic acids is not converted into di-hydroxy stearone, but the unsaturated ketones are so converted more or less completely, so that the product is a mixed product made up in part of the unchanged saturated ketone and in part of the hydroxy ketones pro duced from the unsaturated ketones;

The crude product produced according to this specific example is not greasy and is much harder than that prepared from oleone alone. The crude product may be hard enough for many purposes, but it may be further purified, when desired. It may be partially decolorized and made very hard and brittle by crystallizing from ethyl acetate or isopropyl alcohol, or other suitable solvent.

In the last example, benzol is employed as the solvent since the mixture of ketones is only slightly soluble in naphtha. In general, the solvent should be one in which the ketones are sol uble but which does not react with either the ketones or the sulfuric acid.

In a similar manner, hydroxy ketones can be prepared from other unsaturated ketones, or item mixtures of unsaturated ketones; and mixtures of hydroxy ketones and of saturated ketones can be prepared from mixtures of unsaturated and saturated ketones.

The new hydroxy ketone products of the present invention are more valuable commercial products than the ketones from which they are produced. The ketones themselves are relatively soft and of low melting point and their uses and applications are limited. However, by converting them into hydroxy ketones according to the present invention, the resulting products are much harder and of higher melting point and form valuable commercial substitutes for natural waxes, and particularly for harder waxes.

Throughout the specification and the claims the following terms have been employed to designate the compounds given below:

1. The method of preparing hydroxy ketones, which comprises treating unsaturated ketones -O mono-hydmxy stearone O stearone the unsaturated ketones into ethereal sulfates,-

and hvdrolyzing the ethereal sulfates to produce hydroxy ketones admixed with the saturated ketones. Y

3. The method of preparing hydroxy ketones which comprises dissolving unsaturated ketones containing at least 18 carbon atoms in a solvent which does not react with sulfuric acid, treating the solution with concentrated sulfuric acid to convert the ketones into ethereal sulfates, and hydrolyzing these sulfates to produce hydroxy ketones.

4. The method of preparing hydroxy ketones, which comprises treating with sulfuric acid a solution of unsaturated ketones produced from commercial oleic acid, dissolved in a solvent which does not react with sulfuric acid, thereby converting the unsaturated ketones into the ethereal sulfates, and hydrolyzing the sulfates to form hydroxy ketones.

5. The method of preparing a mixture containing stearone, mono-hydro stearone and dihydroxy stearone, which comprises, treating with sulfuric acid a solution of oleone prepared from commercial oleic acid and stearone in a solvent which does not react with sulfuric acid thereby converting the oleone into the ethereal sulfate, and hydrolyzing the ethereal sulfate.

6. The method of producing hydroxy ketones, which comprises treating ketones containing at least 18 carbon atoms with sulfuric acid to convert the ketones into etheral sulfates in the presence of an organic solvent which does not react with the surfuric acid, and hydrolyzing the ethereal sulfates by the action of hot water to form the hydroxy ketones.

7. As a new product, di-hydroxy stearone.

8. The method of preparing a hydroxy ketone,

, which comprises dissolving oleone in a solvent which does not react with sulfuric acid, treating the solution with sulfuric acid of between and percent concentration, thereby converting the oleone into the ethereal sulfate and then hydrolyzing the ethereal sulfate to form an hydroxy stearone.

9. New wax-like products consisting essentially of ketones, including hydroxy ketones having the general formula R.CO.R1 where R and R1 are aliphatic radicals, each containing at least about 17 carbon atoms.

10.. As new products, hydroxy ketones having the general formula R.C0.R1 where R and R1 are aliphatic radicals, each containing at least about 17 carbon atoms.

. 11. As new products, wax-like products consisting essentially of saturated hydroxy ketones derived from fatty acids from natural fats and having molecular weights depending upon the fatty acids from which derived.

12. As new products, wax-like mixtures of hydroxy ketones having the general formula R.CO.R1 and saturated ketones having the formula R1.CO.R: where R, R1, R1 and R3 are aliphatic radicals, each containing at least about 17 carbon atoms.

13. As a new product, a wax-like mixture consisting essentially of ketones, including di-hydroxy stearone and stearone.

14. As new products, wax-like mixtures consisting essentially of hydroxy ketones having the general formula R.CO.R1, unsaturated ketones having the general formula R2.CO.Ra and saturated ketones having a general formula R4.CO.R$ where R, R1, R2, R3, R4 and R5 are aliphatic radicals, each having at least about 17 carbon atoms.

15. As a new product, a wax-like mixture of ketones consisting essentially of di-lwdroxy stearone, stearone and mono-hydroxy stearone.

16. New wax-like products consisting essentially of saturated ketones and hydroxy ketones including di-hydroxy stearone.

17. As new products, hydroxy ketones having the general formula R.CO.R1 where R and R1 are aliphatic radicals, each containing at least seventeen carbon atoms and either R or R1 contains an OH group.

18. As new products, wax-like mixtures of saturated ketones including hydroxy ketones.

DONALD K; TRESSLER. CARLISLE SCHADE. 

